EP0098159B1 - Preparation of n-phosphonomethylglycine - Google Patents
Preparation of n-phosphonomethylglycine Download PDFInfo
- Publication number
- EP0098159B1 EP0098159B1 EP83303749A EP83303749A EP0098159B1 EP 0098159 B1 EP0098159 B1 EP 0098159B1 EP 83303749 A EP83303749 A EP 83303749A EP 83303749 A EP83303749 A EP 83303749A EP 0098159 B1 EP0098159 B1 EP 0098159B1
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- EP
- European Patent Office
- Prior art keywords
- formyl
- formamide
- reacting
- phosphonomethylglycine
- aminomethylphosphonate
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
Definitions
- This invention relates to the preparation of N-phosphonomethylglycine, a known herbicide and plant growth regulator.
- Herbicides are widely used, for example, by farmers and commercial agricultural companies in order to increase crop yields for staple crops, such as corn, soybeans and rice, and to eliminate weed growth, for example, along highways and railroad rights-of-way.
- Herbicides are effective in killing or controlling unwanted weeds which compete for soil nutrients with the crop plants and, by reason of the factor that they kill weeds, are responsible for improving the aesthetic appearance of, for example, highways and railroad rights-of-way.
- the pre-emergence herbicides are normally incorporated into the soil prior to the emergence of the weed plants from the soil and the post-emergence herbicides are normally applied to plant surfaces after emergence of the weeds or other unwanted plants from the soil.
- N-phosphonomethylglycine One such compound which has been found to be biodegradable, yet which when in salt form is effective as a herbicide and plant growth regulator when employed at lower rates, is N-phosphonomethylglycine. Certain agriculturally effective salts of N-phosphonomethylglycine have been approved for use by the U.S. Government, and, as a consequence, this herbicide has become extremely successful commercially.
- the salts of N-phosphonomethylglycine are the only effective and approved post-emergence herbicides in the field.
- the present commercial compound is the isopropylamine salt of N-phosphonomethylglycine and derivatives thereof.
- N-phosphonomethylglycines can be made in a number of different ways.
- One such method as described in U.S.-A-3,160,632 (Toy et al., December 8, 1964) is to react N-phosphinomethylglycine (glycinemethylenephosphinic acid) with mercuric chloride in a water solvent at reflux temperature, and subsequently separating the reaction products.
- Other methods include the phosphonomethylation of glycine and the reaction of ethyl glycinate with formaldehyde and diethylphosphite. The latter method is described in U.S.-A-3,799,758 (Franz, March 26, 1974).
- the instant invention is thus concerned with a novel method for the production of N-phosphonomethylglycine and specific intermediates.
- the present invention is a process for the preparation of N-phosphonomethylglycine utilizing formaldehyde and formamide as starting materials and which in toto comprises four steps. Some of these steps are specific to certain compounds, and others are generic in nature. For that reason, the invention as a whole will be first described with regard to the specific compounds, and then each of the steps will be treated separately in substantial detail and the generic aspects, where applicable, will be described.
- N-(hydroxymethyl) formamide can be prepared simply by combining formamide and formaldehyde with heating.
- the product obtained is N - bis(hydroxymethyl)formamide, which has the structure:
- N-(hydroxymethyl)formamide can be prepared by inverse addition of formaldehyde to formamide at room temperature while maintaining the pH of the reaction solution between 9 and 10.
- This reaction can be represented as follows, and represents the first step of the process of the invention.
- step (1) one equivalent of formaldehyde is used for every two equivalents of formamide.
- the pH of the reaction solution is critical, and must be maintained at between about 9 and 10.
- the pH can be adjusted by any suitable means, however, it is preferred to use bases such as potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide, with the most preferred base being potassium carbonate.
- step (1) the formaldehyde must be added to the formamide, because it has been found that this is the only way that the desired product, N-(hydroxymethyl)formamide, can be obtained. If the formamide is added to the formaldehyde, the desired end product is not achieved.
- the reaction can be conducted at room temperature, and in that instance, the reaction time is about 4 hours. If heat is used, then of course, the reaction time will be substantially reduced. The use of heat is not essential, however. Desirably, the temperature of the reaction solution will range from about 20 to 25°C.
- N-(hydroxymethyl)formamide is next reacted with a triethylphosphite compound to form diethyl - N - (formyl) - aminomethylphosphonate.
- This reaction can be represented as follows:
- the mole ratio of N-(hydroxymethyl)formamide to triethylphosphite in step (2) of the process of the invention is preferably from 1:1 to 1.1:1.
- the reaction is conducted in the presence of heat and at a temperature sufficient to cause the reaction to go to completion.
- the reactants are heated until ethyl alcohol starts to evolve and this occurs at reflux temperature.
- this temperature is approximately 120-125°C.
- the alcohol is distilled off, leaving the product diethyl - N - (formyl)aminomethylphosphonate as the residue.
- step (2) can also be considered to be a generic process in which the N-(hydroxymethyl)-formamide is reacted with a trialkylphosphite of the formula P(OR) 3 , wherein R is an alkyl radical having from 1-6 carbon atoms, to produce a dialkyl - N - (formyl)aminoethylphosphonate.
- this reaction can be represented as follows:
- the conditions of the reaction when a trialkylphosphite is used instead of triethylphosphite are in general the same as the conditions when triethylphosphite is the compound of choice, i.e., the ratio of N - (hydroxymethyl)formamide to trialkylphosphite is still 1:1, and the reaction is conducted in the presence of heat and at a temperature sufficient to cause the reaction to go to completion.
- the temperature will range from about 80 to 150°C
- the time will range from about 2 to about 3 hours, but the exact temperature and time of the reaction will depend upon the specific nature of the trialkylphosphite compound used.
- Suitable trialkylphosphites for use in the invention include triethylphosphite, tripropylphosphite, tributylphosphite and others of a like nature.
- the process in the third step of the process of the invention comprises reacting diethyl - N - (formyl)aminomethylphosphonate with methylchloroacetate in the presence of a proton-extracting base and a suitable solvent to produce N - (diethylphosphonomethyl) - N - (formyl)glycine methyl ester.
- R 1 is a radical selected from formyl, acetyl, methoxycarbonyl, phenyloxycarbonyl, and benzyl
- R is a radical selected from methyl, ethyl, propyl, butyl, pentyl, and hexyl.
- steps (3a) or (3b) above are carried out in the presence of a suitable solvent, and suitable solvents include tetrahydrofuran, toluene, methylisobutylketone, dimethylformamide, or any other organic solvent of a similar nature.
- suitable solvents include tetrahydrofuran, toluene, methylisobutylketone, dimethylformamide, or any other organic solvent of a similar nature.
- reaction it is essential that the reaction also be carried out in the presence of a proton-extracting base, and suitable bases include sodium hydride and potassium carbonate.
- suitable bases include sodium hydride and potassium carbonate.
- the preferred base for use is sodium hydride.
- the preferred solvent for use in the process described in step (3) above is tetrahydrofuran.
- the mole ratio of dialkyl - N - (substituted)aminomethylphosphonate to methylchloroacetate used in the process of step (3) is 1:1.
- the process is conducted at a sufficient temperature and for a sufficient time for the reaction to go to completion.
- the exact time will vary depending, of course, upon the nature of the starting compound used, however, when diethyl - N - (formyl)aminomethylphosphonate is the starting compound, then the reaction is preferably conducted at a temperature ranging from about 10 to 25°C for about 2 hours.
- Preferred starting compounds for the reaction set forth in step (3) above include diethyl - N - (formyl)aminomethylphosphonate.
- the preferred compounds for use in step (3) of the process of the invention include diethyl - N - (formyl)aminomethylphosphonate, methylchloroacetate, and tetrahydrofuran as a solvent, plus sodium hydride as the proton-extracting base.
- Step (4) in the process of the invention comprises reaction of N-(diethylphosphonomethyl), N-(substituted)glycinemethyl ester with a hydrolyzing agent to form the desired end product, N-phosphonomethylglycine.
- the starting compound in step (4) of the reaction is the product achieved in step (3), and the preferred starting compound is thus N - (diethylphosphonomethyl) - N - (formyl)glycine methyl ester.
- reaction can be stated as follows: wherein R and R 1 are the same as in step 3.
- hydrochloric acid is the preferred hydrolyzing agent.
- suitable hydrolyzing agents include hydrobromic acid and sulfur acid, for example.
- the N-phosphonomethylglycine produced in accordance with the method of step (4) can be separated from the reactants by any suitable means, including filtration of the precipitate.
- the preferred reactants of step (4) are N-(diethylphosphonomethyl) N-(formyl)glycinemethyl ester and hydrochloric acid as the hydrolyzing agent.
- the hydrolyzing agent is preferably used in excess.
- the reaction is preferably conducted at a temperature ranging from about 120 to 125°C, preferably using a mole ratio of the ester to hydrochloric acid of from 1:1 to 5:1.
- N-(hydroxymethyl)formamide has the structure:
- N-(hydroxymethyl)formamide prepared in Example I can be used to synthesize diethyl, N-(formyl)aminomethylphosphonate by the procedure described in Example II.
- the diethyl, N-(formyl)aminomethylphosphonate can be alkylated to give N-(diethylphosphonomethyl), N-(formyl)glycinemethyl ester as described in Example III.
- the product obtained was a cloudy yellow solution which was filtered through celite, washed with tetrahydrofuran and then stripped at 40°C with high vacuum.
- the resulting product was 2.34 g of a cloudy yellow solution.
- Structure was confirmed as N - (diethylphosphonomethyl) - N - (formyl)glycinemethyl ester by GC and MS. (GC is gas chromatography; MS is mass spectroscopy).
- N-(diethylphosphonomethyl) N-(formyl)glycinemethyl ester prepared in Example III can be hydrolyzed to give N-phosphonomethylglycine as described in Example IV.
- N-phosphonomethylglycine compounds which are produced in accordance with the method of the invention, in and of themselves, have herbicidal and plant growth regulating efficacy. However, because the acid form is not in itself very soluble in aqueous solutions, it is preferred to convert these compounds to their salt forms for inclusion into herbicidal compositions. Salt forms which have been found to have high rates of herbicidal activity and plant growth regulating activity are the trialkylsulfonium salts of N-phosphonomethylglycine, such as are disclosed in U.S.-A-4,315,765. Methods of preparation for N-phosphonomethylglycine are described in that patent.
Abstract
Description
- This invention relates to the preparation of N-phosphonomethylglycine, a known herbicide and plant growth regulator.
- Herbicides are widely used, for example, by farmers and commercial agricultural companies in order to increase crop yields for staple crops, such as corn, soybeans and rice, and to eliminate weed growth, for example, along highways and railroad rights-of-way. Herbicides are effective in killing or controlling unwanted weeds which compete for soil nutrients with the crop plants and, by reason of the factor that they kill weeds, are responsible for improving the aesthetic appearance of, for example, highways and railroad rights-of-way. There are a number of different types of herbicides presently sold commercially and these fall into two general categories. The categories are pre-emergence and post-emergence herbicides. The pre-emergence herbicides are normally incorporated into the soil prior to the emergence of the weed plants from the soil and the post-emergence herbicides are normally applied to plant surfaces after emergence of the weeds or other unwanted plants from the soil.
- One of the earliest post-emergence herbicides used commercially was 2,4-D (2,4 - dichlorophenoxyacetic acid). After a number of years of use of this and similar compounds, such as 2,4,5-T (2,4,5 - trichlorophenoxyacetic acid), it was found that certain decomposition products of these herbicides were long lasting and were not biodegradable. While there has been some dispute between governmental agencies and commercial interests regarding the effects of residual products of 2,4-D, 2,4,5-T and similar compounds, the agencies nevertheless restricted the use of these herbicides in the United States some years ago. Since that time, efforts have been made to develop herbicides which are biodegradable into harmless residues within a relatively short time after their application.
- One such compound which has been found to be biodegradable, yet which when in salt form is effective as a herbicide and plant growth regulator when employed at lower rates, is N-phosphonomethylglycine. Certain agriculturally effective salts of N-phosphonomethylglycine have been approved for use by the U.S. Government, and, as a consequence, this herbicide has become extremely successful commercially.
- The salts of N-phosphonomethylglycine are the only effective and approved post-emergence herbicides in the field. The present commercial compound is the isopropylamine salt of N-phosphonomethylglycine and derivatives thereof.
- In field use it is normally applied in amounts of from 0.0112 to 22.4 kg/ha (from 0.01 to about 20 pounds per acre), preferably from 2.24 to 6.72 kg/ha (from 2 to 6 pounds per acre).
- The N-phosphonomethylglycines, and certain soluble salts thereof, can be made in a number of different ways. One such method, as described in U.S.-A-3,160,632 (Toy et al., December 8, 1964) is to react N-phosphinomethylglycine (glycinemethylenephosphinic acid) with mercuric chloride in a water solvent at reflux temperature, and subsequently separating the reaction products. Other methods include the phosphonomethylation of glycine and the reaction of ethyl glycinate with formaldehyde and diethylphosphite. The latter method is described in U.S.-A-3,799,758 (Franz, March 26, 1974). In addition, there is a whole series of patents, relating to N-phosphonomethylglycines, their salts, and derivatives thereof, described as being useful herbicides and plant growth regulators. Such additional patents relating to the N-phosphonomethylglycines, methods of application, methods of preparation, salts, and derivatives, -include U.S.-A-3,868,407, U.S.-A-4,197,254, and U.S.-A-4,199,354, among others.
- Because of the importance of certain salts of N-phosphonomethylglycine as herbicides, other methods of making the compounds are constantly being sought in order to provide improved or alternate methods of manufacture.
- The instant invention is thus concerned with a novel method for the production of N-phosphonomethylglycine and specific intermediates.
- The present invention is a process for the preparation of N-phosphonomethylglycine utilizing formaldehyde and formamide as starting materials and which in toto comprises four steps. Some of these steps are specific to certain compounds, and others are generic in nature. For that reason, the invention as a whole will be first described with regard to the specific compounds, and then each of the steps will be treated separately in substantial detail and the generic aspects, where applicable, will be described.
- Thus, the overall process of this invention comprises the following steps:
- 1) addition reaction of formaldehyde to formamide while maintaining the reaction solution at a pH of between 9 and 10, to form N-(hydroxymethyl)formamide,
- 2) reaction of N-(hydroxymethyl)formamide with triethylphosphite with accompanying heat, to form diethyl - N - (formyl)aminomethylphosphonate,
- 3) reaction of diethyl - N - (formyl)aminomethylphosphonate with methylchloroacetate in the presence of a suitable solvent to form N - (diethylphosphonylmethyl) - N - (formyl)glycinemethyl ester, and
- 4) reaction of N - (diethylphosphonomethyl) - N - (formyl)glycinemethyl ester with a suitable hydrolyzing agent to form N - phosphonomethylglycine.
- The invention will now be discussed on a step by step basis.
-
- This structure can be confirmed by 13C nuclear magnetic resonance. This is not the desired intermediate product for use in the process of the invention.
- It has now been discovered that the desired intermediate product, N-(hydroxymethyl)formamide, can be prepared by inverse addition of formaldehyde to formamide at room temperature while maintaining the pH of the reaction solution between 9 and 10. This reaction can be represented as follows, and represents the first step of the process of the invention.
- In the reaction set forth above, step (1), one equivalent of formaldehyde is used for every two equivalents of formamide. The pH of the reaction solution is critical, and must be maintained at between about 9 and 10. The pH can be adjusted by any suitable means, however, it is preferred to use bases such as potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide, with the most preferred base being potassium carbonate.
- In the process as described in step (1), the formaldehyde must be added to the formamide, because it has been found that this is the only way that the desired product, N-(hydroxymethyl)formamide, can be obtained. If the formamide is added to the formaldehyde, the desired end product is not achieved.
- The reaction can be conducted at room temperature, and in that instance, the reaction time is about 4 hours. If heat is used, then of course, the reaction time will be substantially reduced. The use of heat is not essential, however. Desirably, the temperature of the reaction solution will range from about 20 to 25°C.
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- The mole ratio of N-(hydroxymethyl)formamide to triethylphosphite in step (2) of the process of the invention is preferably from 1:1 to 1.1:1. The reaction is conducted in the presence of heat and at a temperature sufficient to cause the reaction to go to completion. The reactants are heated until ethyl alcohol starts to evolve and this occurs at reflux temperature. When triethylphosphite is used, this temperature is approximately 120-125°C. At this point, the alcohol is distilled off, leaving the product diethyl - N - (formyl)aminomethylphosphonate as the residue.
- The process of step (2) as set forth, can also be considered to be a generic process in which the N-(hydroxymethyl)-formamide is reacted with a trialkylphosphite of the formula P(OR)3, wherein R is an alkyl radical having from 1-6 carbon atoms, to produce a dialkyl - N - (formyl)aminoethylphosphonate. In a generic sense, therefore, this reaction can be represented as follows:
- The conditions of the reaction when a trialkylphosphite is used instead of triethylphosphite are in general the same as the conditions when triethylphosphite is the compound of choice, i.e., the ratio of N - (hydroxymethyl)formamide to trialkylphosphite is still 1:1, and the reaction is conducted in the presence of heat and at a temperature sufficient to cause the reaction to go to completion. In general, the temperature will range from about 80 to 150°C, and the time will range from about 2 to about 3 hours, but the exact temperature and time of the reaction will depend upon the specific nature of the trialkylphosphite compound used. Suitable trialkylphosphites for use in the invention include triethylphosphite, tripropylphosphite, tributylphosphite and others of a like nature.
- The process in the third step of the process of the invention comprises reacting diethyl - N - (formyl)aminomethylphosphonate with methylchloroacetate in the presence of a proton-extracting base and a suitable solvent to produce N - (diethylphosphonomethyl) - N - (formyl)glycine methyl ester.
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- In the formula set forth in 3b above, R1 is a radical selected from formyl, acetyl, methoxycarbonyl, phenyloxycarbonyl, and benzyl, and R is a radical selected from methyl, ethyl, propyl, butyl, pentyl, and hexyl.
- The reaction of steps (3a) or (3b) above are carried out in the presence of a suitable solvent, and suitable solvents include tetrahydrofuran, toluene, methylisobutylketone, dimethylformamide, or any other organic solvent of a similar nature.
- It is essential that the reaction also be carried out in the presence of a proton-extracting base, and suitable bases include sodium hydride and potassium carbonate. The preferred base for use is sodium hydride.
- The preferred solvent for use in the process described in step (3) above is tetrahydrofuran.
- The mole ratio of dialkyl - N - (substituted)aminomethylphosphonate to methylchloroacetate used in the process of step (3) is 1:1.
- The process is conducted at a sufficient temperature and for a sufficient time for the reaction to go to completion. The exact time will vary depending, of course, upon the nature of the starting compound used, however, when diethyl - N - (formyl)aminomethylphosphonate is the starting compound, then the reaction is preferably conducted at a temperature ranging from about 10 to 25°C for about 2 hours.
- Preferred starting compounds for the reaction set forth in step (3) above include diethyl - N - (formyl)aminomethylphosphonate.
- The preferred compounds for use in step (3) of the process of the invention include diethyl - N - (formyl)aminomethylphosphonate, methylchloroacetate, and tetrahydrofuran as a solvent, plus sodium hydride as the proton-extracting base.
- Step (4) in the process of the invention comprises reaction of N-(diethylphosphonomethyl), N-(substituted)glycinemethyl ester with a hydrolyzing agent to form the desired end product, N-phosphonomethylglycine. The starting compound in step (4) of the reaction is the product achieved in step (3), and the preferred starting compound is thus N - (diethylphosphonomethyl) - N - (formyl)glycine methyl ester.
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-
- Any hydrolyzing agent can be used in step (4) of the reaction, however, hydrochloric acid is the preferred hydrolyzing agent. Other suitable hydrolyzing agents include hydrobromic acid and sulfur acid, for example. The N-phosphonomethylglycine produced in accordance with the method of step (4) can be separated from the reactants by any suitable means, including filtration of the precipitate.
- The preferred reactants of step (4) are N-(diethylphosphonomethyl) N-(formyl)glycinemethyl ester and hydrochloric acid as the hydrolyzing agent. The hydrolyzing agent is preferably used in excess.
- When the preferred compounds are used, the reaction is preferably conducted at a temperature ranging from about 120 to 125°C, preferably using a mole ratio of the ester to hydrochloric acid of from 1:1 to 5:1.
- This invention will be more readily understood by reference to the following examples.
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- It can be prepared in the laboratory by the dropwise addition of 1 part 41 % formaldehyde to 2 parts formamide. This reaction may be carried out as follows:
- Two grams (g) of anhydrous potassium carbonate were added to 32.4 g of 41% formaldehyde. This formaldehyde/potassium carbonate solution was then added dropwise to 40.0 g of 98% formamide at room temperature and then stirred for 1 hour. The resulting solution was stripped, washed once with acetone and methanol, dried over sodium sulfate, filtered and stripped again. The product obtained was 51.3 g of a clear liquid. 13c NMR supported the proposed structure: N-(hydroxymethyl)formamide. (13C NMR is Carbon 13 nuclear magnetic resonance).
- The N-(hydroxymethyl)formamide prepared in Example I can be used to synthesize diethyl, N-(formyl)aminomethylphosphonate by the procedure described in Example II.
- 30.9 ml of triethyl phosphite were added dropwise to 22.5 g of N-(hydroxymethyl)formamide in a reaction flask. Room temperature was maintained during the addition. The reaction mixture was heated to reflux and ethanol and the excess triethyl phosphite were distilled off. The resulting material was 30.0 g of a clear orange liquid hypothesized to be about 54% diethyl, N-(formyl)aminomethylphosphonate. 13C NMR, IR and proton IMR supported the proposed structure.
- The diethyl, N-(formyl)aminomethylphosphonate can be alkylated to give N-(diethylphosphonomethyl), N-(formyl)glycinemethyl ester as described in Example III.
- To 0.32 g (0.0132 mole) of dry sodium hydride taken in 10 ml of tetrahydrofuran was added 2.35 g of diethyl N-(formyl)aminomethylphosphonate in 10 ml tetrahydrofuran and then stirred at room temperature under N2 for 30 minutes. To the clear solution obtained was added 1.3 g (0.012 mole) of methylchloroacetate and stirred at ambient temperature for 12 hours.
- The product obtained was a cloudy yellow solution which was filtered through celite, washed with tetrahydrofuran and then stripped at 40°C with high vacuum. The resulting product was 2.34 g of a cloudy yellow solution. Structure was confirmed as N - (diethylphosphonomethyl) - N - (formyl)glycinemethyl ester by GC and MS. (GC is gas chromatography; MS is mass spectroscopy).
- The N-(diethylphosphonomethyl) N-(formyl)glycinemethyl ester prepared in Example III can be hydrolyzed to give N-phosphonomethylglycine as described in Example IV.
- 0.9 g of N-(diethylphosphonomethyl), N-(formyl)glycinemethyl ester and 20 ml of concentrated hydrochloric acid were taken in a reaction flask and refluxed for 16 hours. The solution was stripped to dryness and 2.3 ml of ethanol was added. A precipitate formed and was filtered. Product obtained was 400 mg of a white solid which was hypothesized to be N-phosphonomethylglycine. Structure was confirmed by high pressure liquid chromatography, NMR, and 13c NMR.
- The N-phosphonomethylglycine compounds which are produced in accordance with the method of the invention, in and of themselves, have herbicidal and plant growth regulating efficacy. However, because the acid form is not in itself very soluble in aqueous solutions, it is preferred to convert these compounds to their salt forms for inclusion into herbicidal compositions. Salt forms which have been found to have high rates of herbicidal activity and plant growth regulating activity are the trialkylsulfonium salts of N-phosphonomethylglycine, such as are disclosed in U.S.-A-4,315,765. Methods of preparation for N-phosphonomethylglycine are described in that patent.
Claims (11)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AT83303749T ATE21903T1 (en) | 1982-06-30 | 1983-06-29 | PRODUCTION OF N-PHOSPHONOMETHYLGLYCINE. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/393,574 US4422982A (en) | 1982-06-30 | 1982-06-30 | Method for preparation of N-phosphonomethylglycine |
US393574 | 1982-06-30 |
Publications (3)
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EP0098159A2 EP0098159A2 (en) | 1984-01-11 |
EP0098159A3 EP0098159A3 (en) | 1984-03-21 |
EP0098159B1 true EP0098159B1 (en) | 1986-09-03 |
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EP83303749A Expired EP0098159B1 (en) | 1982-06-30 | 1983-06-29 | Preparation of n-phosphonomethylglycine |
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US (1) | US4422982A (en) |
EP (1) | EP0098159B1 (en) |
JP (1) | JPS5913795A (en) |
KR (1) | KR870001334B1 (en) |
AT (1) | ATE21903T1 (en) |
AU (1) | AU555801B2 (en) |
BR (1) | BR8303370A (en) |
CA (1) | CA1205487A (en) |
CS (2) | CS244939B2 (en) |
DD (1) | DD212966A5 (en) |
DE (1) | DE3365866D1 (en) |
DK (1) | DK292283A (en) |
ES (2) | ES8504209A1 (en) |
HU (1) | HU194256B (en) |
IL (3) | IL69112A (en) |
PL (1) | PL140912B1 (en) |
RO (1) | RO86524B (en) |
ZA (1) | ZA834740B (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES8603901A1 (en) * | 1983-07-27 | 1986-01-01 | Rhone Poulenc Agrochimie | Herbicides of the sulfon imide-type with an aminomethylphosphonic group. |
FR2560198B1 (en) * | 1984-02-23 | 1987-05-07 | Rhone Poulenc Agrochimie | ESTERS OF THE N-PHOSPHONOMETHYLGLYCIN FAMILY AND THEIR USE FOR THE PREPARATION OF KNOWN HERBICIDES |
US4548759A (en) * | 1984-08-30 | 1985-10-22 | Stauffer Chemical Company | Preparation of phosphonomethylated amino acids |
US4548758A (en) * | 1984-08-30 | 1985-10-22 | Stauffer Chemical Company | Preparation of phosphonomethylated amino acids |
US4921991A (en) * | 1985-02-22 | 1990-05-01 | Guy Lacroix | Preparation of esters of the N-phosphonomethylglycine and the N-phosphonomethyl glycines |
FR2611204B1 (en) * | 1987-02-19 | 1989-05-05 | Rhone Poulenc Agrochimie | INTERMEDIATE COMPOUNDS USEFUL FOR THE PREPARATION OF HERBICIDES |
US4830788A (en) * | 1987-11-20 | 1989-05-16 | Crompton & Knowles Corporation | Process for preparation of substituted-aminomethylphosphonic acids |
WO2014012987A1 (en) | 2012-07-17 | 2014-01-23 | Straitmark Holding Ag | Method for the synthesis of aminoalkylenephosphonic acid |
ES2609488T3 (en) | 2012-07-17 | 2017-04-20 | Straitmark Holding Ag | Method for the synthesis of N- (phosphonomethyl) glycine |
US20150232493A1 (en) | 2012-07-17 | 2015-08-20 | Straitmark Holding Ag | Method for the synthesis of alpha-aminoalkylenephosphonic acid |
CN104854117B (en) | 2012-07-17 | 2018-12-25 | 孟山都技术有限责任公司 | Method for synthesizing N- phosphonomethyliminoacidetic acidetic |
CN110771607A (en) * | 2019-10-09 | 2020-02-11 | 集美大学 | N-hydroxymethyl amide antibacterial agent and preparation method thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE764270A (en) * | 1970-03-20 | 1971-08-02 | Benckiser Gmbh Joh A | NIRIL-TRIS- (METHYLENEPHOSPHONIC) ACID AND PROCESS FOR PREPARATION |
US3853530A (en) * | 1971-03-10 | 1974-12-10 | Monsanto Co | Regulating plants with n-phosphonomethylglycine and derivatives thereof |
US4053505A (en) * | 1976-01-05 | 1977-10-11 | Monsanto Company | Preparation of n-phosphonomethyl glycine |
CH647528A5 (en) * | 1978-10-27 | 1985-01-31 | Bcap Biolog Chem Act Pat | PROCESS FOR THE PREPARATION OF N-phosphonomethylglycine. |
HU184601B (en) * | 1979-07-09 | 1984-09-28 | Alkaloida Vegyeszeti Gyar | Process for producing n-/phosphono-methyl/-glycine |
-
1982
- 1982-06-30 US US06/393,574 patent/US4422982A/en not_active Expired - Fee Related
-
1983
- 1983-06-23 BR BR8303370A patent/BR8303370A/en unknown
- 1983-06-24 DK DK292283A patent/DK292283A/en not_active Application Discontinuation
- 1983-06-28 PL PL1983242729A patent/PL140912B1/en unknown
- 1983-06-28 AU AU16316/83A patent/AU555801B2/en not_active Ceased
- 1983-06-28 CA CA000431323A patent/CA1205487A/en not_active Expired
- 1983-06-28 RO RO111440A patent/RO86524B/en unknown
- 1983-06-28 JP JP58115298A patent/JPS5913795A/en active Pending
- 1983-06-29 KR KR1019830002953A patent/KR870001334B1/en not_active IP Right Cessation
- 1983-06-29 EP EP83303749A patent/EP0098159B1/en not_active Expired
- 1983-06-29 ZA ZA834740A patent/ZA834740B/en unknown
- 1983-06-29 DD DD83252532A patent/DD212966A5/en unknown
- 1983-06-29 IL IL69112A patent/IL69112A/en unknown
- 1983-06-29 AT AT83303749T patent/ATE21903T1/en not_active IP Right Cessation
- 1983-06-29 DE DE8383303749T patent/DE3365866D1/en not_active Expired
- 1983-06-29 IL IL80523A patent/IL80523A/en unknown
- 1983-06-29 ES ES523690A patent/ES8504209A1/en not_active Expired
- 1983-06-29 HU HU832357A patent/HU194256B/en unknown
- 1983-06-29 CS CS834849A patent/CS244939B2/en unknown
-
1984
- 1984-04-20 CS CS843017A patent/CS244948B2/en unknown
- 1984-11-30 ES ES538163A patent/ES538163A0/en active Granted
-
1986
- 1986-11-06 IL IL80523A patent/IL80523A0/en unknown
Also Published As
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ES523690A0 (en) | 1985-04-01 |
CA1205487A (en) | 1986-06-03 |
IL69112A (en) | 1987-10-20 |
ES8507565A1 (en) | 1985-09-01 |
CS244939B2 (en) | 1986-08-14 |
DK292283D0 (en) | 1983-06-24 |
BR8303370A (en) | 1984-02-07 |
EP0098159A3 (en) | 1984-03-21 |
AU1631683A (en) | 1984-01-05 |
HU194256B (en) | 1988-01-28 |
KR840005158A (en) | 1984-11-05 |
ES8504209A1 (en) | 1985-04-01 |
ATE21903T1 (en) | 1986-09-15 |
DE3365866D1 (en) | 1986-10-09 |
EP0098159A2 (en) | 1984-01-11 |
RO86524B (en) | 1985-03-30 |
CS244948B2 (en) | 1986-08-14 |
DK292283A (en) | 1983-12-31 |
JPS5913795A (en) | 1984-01-24 |
DD212966A5 (en) | 1984-08-29 |
IL80523A0 (en) | 1987-02-27 |
IL69112A0 (en) | 1983-10-31 |
KR870001334B1 (en) | 1987-07-18 |
IL80523A (en) | 1987-10-20 |
PL242729A1 (en) | 1984-07-16 |
RO86524A (en) | 1985-03-15 |
US4422982A (en) | 1983-12-27 |
AU555801B2 (en) | 1986-10-09 |
ZA834740B (en) | 1984-04-25 |
PL140912B1 (en) | 1987-06-30 |
ES538163A0 (en) | 1985-09-01 |
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